Process for breaking petroleum emulsions



Patented July 29, 1952 PROCESS Eon BREAKING PETROLEUM EMULSIONS Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application February 8, 1952, Serial No. 270,766

This invention relates to petroleum emulsions of the water-in-oil type that are commonlyreferred to as cut oil, roily oil, emulsifiedoil, etc., and which comprise line droplets ofnaturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase otthe emulsion.

One object of my invention is. to provide a novel process for breaking or resolving emulsions of the kind referred to.

Another object of my invention is 'to provide an economical and rapid process forseparating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines.

Controlled emulsification and subsequent demulsification under th conditions just mentioned are of significant value in removing impurities particularly inorganic salts from pipeline oil.

Demulsification as contemplated in the present application includes the preventive step of commingling the demulsifier with. the aqueous component which would or might subsequently become either phase of the emulsion, in absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component.

The demulsifying agent employed in the present process is a fractional ester obtained from a polycarboxy acid and a diol obtained by the oxypropylation of dihydroxylated ethers of glycerol with the proviso that the ether radical have less than 8 carbon atoms and is preferably obtained from a water-soluble aliphatic al- 11 Claims. (01. 252-340) cohol but may be obtained from an alicyclic al- I cohol suchas cyclohexanol or from a phenol such as hydroxybenzene or cresol. Glycerol ethers which are available for this type of synthesis ..includeglycerol alpha-allyl ether, glycerol alphaethyl ether, glycerol alpha-isopropyl ether, glycerol alpha-phenyl ether, etc. As an example of a suitable reactant referenc is made specifically to glycerol alpha-isopropyl ether. Momentarily ignoring certain variants of structure which will be considered subsequently the. demulsifier may be exemplified by the following formula:

in which n and 'n' arenumerals including 0 with the proviso that n plus n equals a sum varying from 15 to n" is a whole number notover 2 and R is the radical of the polycarboxy radical and preferably free from any radicals having more than 8 uninterrupted carbon atoms in a single group, and with the further proviso that the parent diol prior to esterification be waterinsoluble and kerosene-soluble.

The present application is a continuation-inpart of my copending application Serial No. 179,400, filed August 14, 1950, now abandoned.

Attention is directed to the C. M. Blair, Jr. Patent No. 2,562,878, dated August 7, 1951, the application for which was co-pending with my application Serial No. 179,400 noted above and in which there is described, among other things, a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of an esterification prod- -uct of a dicarboxylic acid and a polyalkylene glycol'in which the ratio of equivalents'of polybasic acid to equivalents of polyalkylene glycol is in the range of 0.5 to 2.0, in which the alkylene group has from 2 to 3 carbon atoms, and in which the molecular weight of the product is between 1,500 to 4,000.

Similarly, there have been used esters of dicarboxy acids and polypropylene glycols inwhich 2 moles of the dicarboxy acid ester have been reacted with onemole of a polypropylene glycol having a molecular weight, for example, of 2,000 so as to form an acidic fractional ester. Examination of what is said subsequently herein as well as the hereto appended claims in comparison with the previous example will show the line of delineation between such somewhat comparable compounds. Of greater significance, however, is what. is said subsequentlyin regard to the structure of the parent diol as compared to polypropylene glycols whose molecular'weights may vary from 1,000 to 2,000.

As previously stated it is my preference to employ derivatives in which the ether group is supplied by an aliphatic alcohol, preferably having at least 3 carbon atoms and being watersoluble, such as propyl alcohol, butyl alcohol, or

amyl alcohol. In the case of butyl or amyl alcohols'some of the isomers are water-soluble to v the extent that they show solubility of at least afew per cent at room temperature. Other al- 1 alcohol.

3 cohols which can be employed include tetrahydropyran-Z-methanol and tetrahydrofurfuryl Such ethers can be prepared in various ways and one of the simplest procedures involves the treatment of an alcohol with a mole of glycide. Other procedures involve a similar reaction in which the alcohol is treated with epichlorohydrin under conditions so a substituted ethylene or propylene oxide is obtained, 1. e., a compound having an epoxy ring which is then reacted with water to yield the corresponding glycerol ether. Such intermediates containing the epoxy ring are sometimes referred to as glycidyl ethers.

As to patents that illustrate such procedure see U. S. Patents Nos. 1,959,930, 2,089,569, 2,164,007, 2,181,100, 2,221,818, 2,258,892, 2,314,039, 2,380,185, 2,453,634, 2,413,860, 2,010,726, and British Patent No. 518,057.

See also pamphlet entitled Epichlorohydrin, issued by Shell Chemical Corporation, New York city, New York..

For convenience, what is said hereinafter will be divided into five parts:

Part 1 is concerned with the preparation of the oxpropylation derivatives of the glycerol ether type of diol;

Part 2 is concerned with the preparation of the esters from the oxypropylated derivative;

Part 3 is concerned with a consideration of the structure of the glycerol ether type of diols which is of significance in light of what is said subsequently;

Part 4 is concerned with the use of the products herein described as demulsifiers for breaking water-in-oil emulsions; and

Part 5 is concerned with certain derivatives which can be obtained from the oxypropylated diols. In some instances, such derivatives are obtained by modest oxyethylation preceding the oxypropylation step. or oxypropylation followed by oxyethylation. This results in diols havin somewhat difierent properties which can then be reacted with the same polycarboxy acids or anhydrides described in Part 2 to give effective demulsifying agents. For this reason a description of the apparatus makes casual mention of oxyethylation. brief mention of the use of glycide.

PART 1 For a number of well known reasons equipment, whether laboratory size, semi-pilot plant size, pilot plant size, or large scale size, is not as a rule designed for a particular alkylene oxide. Invariablyand inevitably, however, or particularly in the case of laboratory equipment and pilot plant size the design is such as to use any of the customarily available alkylene oxide, i. e., ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, styrene oxide, etc. In the subsequent description of the equipment it becomes obvious that it is adapted for oxyethylation as well as oxypropylation.

Oxypropylations are conducted undera Wide variety of conditions, not only in regard to presence or absence of catalyst, and the kind of catalyst, but also in regard to the time of reaction, temperature of reaction, speed of reaction, (pressure during reaction, etc. Flor instance, oxyalkylations can be conducted at temperatures up to approximately 200- C. with pressures in For the same reason there is square inch. They can be conducted also at temperatures approximating the boiling point of water or slightly above, as for example to C. Under such circumstances the pressure will be less than 30 pounds per square inch unless some special procedure is employed as is sometimes the case, to wit, keeping an atmosphere of inert gas such as nitrogen in the vessel during the reaction. Such low-temperature-low reaction rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664, to H. R. Fife et a1., dated September 7, 1948. Low temperature, low pressure oxypropylations are particularly desirable where the compound being subjected to oxypropylation contains one, two or three points of reaction only, such as monohydric alcohols, glycols and triols.

Since low pressure-low temperature reaction speed oxypropylations require considerable time, for instance, 1 to 7 days of 24 hours each to complete the reaction they are conducted as a rule whether on a laboratory scale, pilot plant scale, or large scale, so as to operate automatically. The prior figure of seven days applies especially to large-scale operations. I have used conventional equipment with two added automatic features: (a) a solenoid controlled valve which shuts ofi the propylene oxide in event that the temperature gets outside a predetermined and set range, for instance, 95 to 120 C.,. and (b). another solenoid valve which shuts ofi the propylene oxide (or for that matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to 35 pounds. Otherwise, the equipment is substantially the same as is commonly employed for this purpose where the pressure of reaction is higher, speed of reaction is higher, and time of reaction is much shorter. In such instances such automatic controls are not necessarily used.

Thus, in preparing the various examples Ihave found it particularly advantageous to use laboratory equipment or pilot plant which is designed to permit continuous oxyalkylation whether it be oxypropylation or exyethylation. With certain obvious changes the equipment can be used also to permit oxyalkylation involving the use of glycide where no pressure is involved except the vapor pressure of a solvent, if any, which may have been used as a diluent.

As previously pointed out the method of usin propylene oxide is the same as ethylene oxide. This point is emphasized only for the reason that the apparatus is so designed and constructed as to use either oxide.

The oxypropylation procedure employed in the preparation of the oxyalkylated derivatives has been uniformly the same, particularly in light of the fact that a continuous automatically-controlled procedure was employed. In this procedure the autoclave wasa conventional autoclave made of stainless steel and having a capacity of approximately 15 gallons and a working pressure of one thousand pounds gauge pressure. This pressure obviously is far beyond any requirement as far as propylene oxide goes unless there is a reaction of explosive violence involved due to accident. The autoclave was equipped with the conventional devices and openings, such as the variable-speed stirrer operating at speeds from 50 R. P, M. to 500 R. P. M.; thermometer well and thermocouple for mechanical thermometer; emptying outlet; pressure gauge, manual vent line; charge hole for initial reactants; at least one connection for introducing the alkylene oxide, such as propylene oxide or ethylene oxide, to the bottom autoclave having a small capacity, for instance,

approximately 3 liters in one case and about 1% gallons in another case, was used.

Continuous operation, or substantially continuous operat'ion, was achieved by the use of a separate container to hold the alkylene oxide being employed, particularly propylene oxide. In. conjunction with the smaller autoclave,'th'e container consists essentially 'of a laboratory bomb having a capacity of about one-half gallon, or

somewhat in excess thereof. In some instances a. larger bomb was used, to wit, one having a capacity of about one gallon. [This bomb was equipped, also, with an inlet for charging, and an eductor tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. A bomb having a capacity of aboutfiO pounds was used in connection with the -gallon autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer, connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use. The connections between the bomb and the autoclave were flexible stainless steel hose or tubing so that continuous weighings could be made without breaking or making any connections. This applies also'to the nitrogen line, which was used to pressure the bombreservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass protective screens, etc.

' Attention is directed again to what has been said previously in regard to-automatic controls which shut ofi the propyleneoxide in event temperature of reaction passes out of the predetermined range or if pressure in the autoclave passes out of predetermined range. I

With this particular arrangement practically all oxypropylations become uniform in that the reaction temperature was held within a. fewde- .grees of any selected point, for instance, if 105 C.

was selected as the, operating temperature the maximum point would be at the most 110C. or 112 C., and the lower point would be 95 or possibly 98 C. Similarly, the pressure was held at approximately pounds within a 5-pound variation one way or the other, but might drop to practically zero, especially where no solvent such as xylene is employed. The speed of reaction was comparatively slow under such conditions as compared with oxyalkylations at 200 C." Numerous reactions were conducted in whichthe time of a series. In some instances the reaction may take place in considerably less time, i. e., 24

hours or less, as far as a partial'oxypropylation is concerned. The minimum time recorded was about a 3-hour period in a single step. Reactions indicated as being complete in 10 hours may have been complete in a lesser period offltime in light a :shorter period of .time,.,for, ins tance.;4=.to.5 hours: Inthe. addition of propylene oxide. in the, autoclaveequipment as far: as possible the valves were set so all the propylene oxide if fed continuously would be added'at a rate so that the predetermined amount would react within the first 15 hours of the 24-hour period or twothirds of any shorter period. This meantthat if the reaction was interrupted automatically for a period oftime for pressure to drop or temperature to drop the predetermined amount of oxide would still be added in most instances well within the predetermined time period. Sometimes where the addition was a comparatively small amount in a 10-hour period there would be an unquestionable speeding up of the reaction, by simply repeating the examples and using 3, 4, or 5 hours instead of 10. hours.

When operating at a comparatively high temperature, for instance, between 150 to 200 C..

an unreacted alkylene oxide such as propylene oxide, makes its presence felt in the increase in pressure or the consistency of a higher pressure. However, at a low enough'temperature it may happen that the propylene oxide goes in asa liquid. .If so, and if it remains unreacted there. is, of course, an inherent danger and appropriate steps must be taken to safeguard against this possibility; if need be a sample must be withdrawn and examined for unreacted propylene oxide. One obvious procedure, of course,

is to oxypropylate at a modestly higher temperature, for instance, at to C. Unreacted oxide afiects determination of the acetyl or hydroxyl value of the hydroxylated compound obtained.

The higher the molecular weight of the compound, i. e., towards the latter stages of reaction, the longer the time, required tov add a given amount .of oxide. One possible explanation is that the molecule, being larger, the opportunity for random reaction is decreased. Inversely, the lower the molecular weight the faster the reaction takes place. For this reason, sometimes at least, increasing. the concentration of the catalyst does not appreciably speed upv the reaction, particularly when the product subjected to oxyalkylation has a comparatively high molecular weight. However, as has been pointed out previously, operating at a low pressure and a low temperature even in large scale operations as much as a week or ten days time may lapse to obtain some of the higher molecular weight derivatives from monohydric or dihydric maamount of propylene oxide had passed into the reaction the scale movement through a time operating device was set for either one to two hours so that reaction continued for l to 3 hours after the final addition of the last propylene oxide 'and thereafter the operation was shut down. This particular device is particularly suitable for use on larger equipment than laboratory size autoclaves, to wit, on semi-pilot plant 'or pilot plant size, as well as on large scale size. This final stirring period is intended to avoid the presence of unreacted oxide.

N In this sort of operation, of course, the temperature range was controlled automatically by either use of cooling water, steam, or electrical of the automaticequipment employed. This.ap.-....,

heat, so .as to raise. or.lower the temperature. The pressuring ofthe propylene oxide into the point of water.

tion a sample was taken and oxypropylation pro- 7 reaction vessel was also automatic insofar: that the feedstream was set for a. slow continuous run which'was shutoff in casethe pressure passed a predetermined .pointas previously set out. All the points of design, construction, etc., were conventional including the gases, check valves and entire equipment. As far as I am aware at least two firms, and possibly three, specialize in autoclave equipmentsuch as I have employed in the laboratory, and are prepared to furnish equipment of this same kind. Similarly pilot plant equipment is available. This point is simply made as precaution in the direction of safety. Oxyalkylatlons, particularly involving ethylene oxide, glycide, propylene oxide, etc.,

should not be conducted except in equipment specifically designed for the purpose.

Example 111 .The particular autoclave. employed was. one with a capacity of approximately 15 gallons, or on the average of about 120 poundsof reaction mass. The speed of the stirrer could be varied from 150 to 350 R. P. M. 8 /2 pounds of glycerol alpha isopropyl ether were charged into the autoclave along with one pound of sodium -hydroxide. The reaction pot was flushed out with nitrogen. The autoclave was sealed, the automatic devices adjusted and set for injecting'a total of 58 pounds of propylene oxide inapproximately -a 5-hour period. The pressure regulator was set for a maximum of 35 pounds per square inch. This meant that the bulk of the reaction could take place, and probably did take place, at a lower pressure. This comparatively low pressure was the result of the fact that considerable catalyst was present, the propylene oxide was added comparatively slowly and, more important, the selected temperature range was 205 to 215-F. (about the boiling point of water). The'initial introduction of propylene oxide was not started until the heating devices had raised the temperature to approximately the boiling At the completion of the reacceeded as in Example 211, immediately succeeding. 1 a

Example 2a 59.5 pounds of the reaction mass identified as ducted in substantially the same manner in regard to pressure and temperature as in Example la, preceding, except that the reaction was complete in slightly less time, i. e., 4 hours instead 8 pylation was continued as described in Example 301, following.

J Example 3a cerned were substantially the same as in Example 1a, preceding. The reaction time was the same as in Example la and a little more than in Example 2a, i. e., 5 hours. At the completion of the reaction part of the reaction mass was withdrawn and the remainder subjected to oxypropylation as described in Example 411, succeeding.

Example 4a Slightly over 70 pounds of the reaction mass were permitted to remain in the autoclave. No additional catalyst was introduced. Slightly over 15.5 pounds of propyleneoxide were introduced in the same manner as described in Example la, preceding. Conditions in regard to temperature and pressure were substantially the same. In this instance the oxide was introduced in slightly less than 6 hours. At the end of the reaction period part of the sample was withdrawn and the remainder of the reaction mass subjected to further oxypropylation as described in example 50., succeeding.

Example 511 Approximately pounds of the reaction mass were permitted to remain in the autoclave. No additional catalyst was introduced. Slightly over 36.5 pounds of propylene oxide were added. The conditions of temperature and pressure were substantially the same as preceding. Note, however, that due to further dilution of catalyst approximately twice as long was required as in previous oxypropylations, i. e., 10 hours. Oxypropylation was continued as described in Example 6a, succeeding.

, f 'Exctmple'da Approximately 68 pounds of reaction mass were permitted to stay in the autoclave. This was subjected to reaction with slightly under 26 pounds of propylene oxide. Conditions of reaction were substantially the same as described in Examplesla as far as temperature and pressure were concerned. The period required for the addition of th'e oxide was 8 hours.

What has been said herein is presented in tabular form in Table 1 immediately following,

with some added'information as to molecular of 5 hours. At the end of the reaction period weight and as to solubility of the reaction product part of the sample was withdrawn and oxypro- 00 in water, xylene and kerosene.

TABLEl Composition Before Composition at End 1 Max l T Y y es. i111 EX- H. C. Oxide Cata- Them. .11. 0. Oxide Gata- Deter- TERI-1?" s Hr Amt, Amt.,' 'lyst, Mol. An1t., Amt., lyst, min. sq. in.

Lbs. Lbs. Lbs. Wt'. Lbs; Lbs. Lbs.

8.50 1.0 1,0413. s15- 5s.0 1.0 704 205-215 35 5 7.50 51.12 .538 1, s14 7.50 94.12 .83 1,075 205-215 35 4 4.97 52.44 .59 2,550 I 4.97 89.69 .59 1,320 205 215 s5 5 3.59, 50.02 .44 3,125 3.69; $2.37 .44 1,650 205-215 35 5% The hydroxylated compound is glycerol alpha isopropyl ether.

acetyl or hydroxyl value.

9. Example 1a was soluble in water, soluble in xylene and somewhat dispersible' or somewhat soluble in kerosene. Examples 2a through'fia, inclusive, were all insoluble in water, but completely soluble in xylene and kerosene.

The final product, i. e., at the end of the oxypropylation step, was somewhat viscous very pale straw-colored fluid which was water insoluble. This is characteristic of all various end products obtained in this series. These products were, of course, slightly alkaline due to the residual caustic soda employed. This would also be the case if sodium methylate were used as a catalyst. Y

Speaking of insolubility in water or solubility in kerosene, such solubility test can be made simply by shaking small amounts of the materials in a test tube with water, for instance, using 1% to 5% approximately based on the amount of water present.

Needless to say, there is no complete conversion of propylene oxide into the desired hydroxylated compounds, This isindicated by the fact that the theoretical molecular weight based on a statistical average is greater than the molecular weight calculated by usual methods on basis of Actually, there is no completely satisfactory method for determining molecular weights of these types of compounds with a high degree of accuracy when the molecular weights exceed 2,000. In some instances the acetyl value or hydroxyl value serves as satisfactorily as an index to the molecular weight asany other procedure, subject to the above limitations, and especially in the higher molecular weight range. If any dilficulty is encountered in the manufacture of the esters as described in Part 2 the stoichiometrical amount of acid or acid compound should be taken which corresponds to the indicated acetyl or hydroxyl value. This matter has been discussed in the literature and is a matter of common knowledge and requires no further elaboration. In fact, it is illustrated by some of the examples appearing in the patent previously mentioned.

Using a smaller autoclave, i. e., one having a capacity slightly less than one gallon, I have prepared a number of similar compounds from glycerol alpha butanol ether obtained by reacting normal butanol with glycerol, and also from glycerolalpha pentanol-3 ether obtained by reacting pentanol-3 with glycide. These ethers were oxypropylated in substantially the same manner and under substantially the same conditions as Examples la through 6a, preceding. For sake of brevity the data are summarized in the following table:'

The above products were comparable in physical appearance although in some instances some- 10 what darker than those derived from the isopropyl ether.

Restating the type of compound herein specified one'need only rewrite the first formula above in which the isopropyl group is replaced by the radical R, thus:

in which all the various characters have their previous significance with the added proviso that R is a radical having lessthan 8 carbon atoms derived from'an aliphaticalcohol, alicyclic alcohol, or phenol, such as those previously mentioned and, additionally, benzyl alcohol or the hydrogenated analog. Attention is directed further to the fact that there'is only one ether linkage uniting the alcohol radical with the glycerol radical. This'is to differentiate from products obtained by employing the same alcohols herein described and first subjecting them to oxyalkylation with ethylene oxide, propylene oxide, butylene oxide or the like, or a mixture of the same. Such derivatives obtained from the ether alcohols as distinguished from the alcohols represent an entirely different variety for the present purpose. For instance, reference is made to such materials as dipropylene glycol isopropyl ether, tripropylene glycol isopropyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and tripropylene glycol n-butyl ether, all of which are made commercially.

Most of the methods which form ethers from glycerol result in the ether. radical being in the alpha position. Isomers in which the ether radical is in the beta position'can be preparedand are just as satisfactory but the cost of preparation does not justify their use for the present purpose. They are, of course,- the obvious equivalents.

Reference is made to the fact that R, is characterized as a hydrocarbon radical. Needless to say in at least two of the alcohols referred to, i. e., tetrahydrOpyran-Z-methanol and tetrahydrofurfuryl alcohol there is an oxygen atom in the alcohol radical. This oxygen atom .in no way interferes with the group functioning in the same manner that a hydrocarbon group, for instance an propyl or butyl-group, would function. 7 Accordingly, compounds derived from these alcohols are the full equivalents of thosein which the alcohols do not contain such an oxygen atom and are intended to be included within the invention as such equivalents.

PART 2 As previously pointed out the present invention is concerned with acidic esters obtained from the oxypropylated' derivatives described in Part 1, immediately preceding, and polycarboxy acids, particularly dicarboxy acids such as adipic acid, phthalic acid, or anhydride, succinic acid, diglycollic acid, sebacic acid, azelaic acid, aconitic acid, maleic acid or anhydride, citraconic acid or anhydride, maleic acid or anhydride adducts as obtained by the Diels-Alder reaction from reactants such as maleic anhydride and cyclopentadiene. Such acids should be heat stable so they are not decomposed during esterification. They may contain as many as 36 carbon atoms as, for example, the acids obtained by dimerization of unsaturated fatty acids, unsaturated monooarboxy fatty acids, or unsaturated monocarboxy acids having 18 carbon atoms. Reference tothe acid in the hereto appended claims obviously includes the anhydrides or any other obvious equivalents. My preference, however, is to use polycarboxy acids having not over *8 carbon atoms.

The production of esters including acid esters (fractional esters) from polycarboxy acids and lycols or other hydroxylated compounds is well known. Needless to say various compounds may be used such as the low molal ester, the anhydride, the acyl'chloride, etc. However, for purpose of economy it is customary to u'seeither'the acid or the anhydride. A conventional procedure is employed. On alaboratory scale one can employ a resin pot of the kind described in U. S. Patent No. 2,499,370, dated March 7, 1950,,to De Groote and Keiser, and particularly with one more opening to permit the usev of a porous spreader if hydrochloric acid gas isto be'used as a catalyst. Such device or absorption spreader consists of minute Alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as para-toluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange oxypropylated compounds, and particularly likely to do so if the esterification temperature is too high. In the case of polycarboxy acids such as diglycollicacid, which is strongly acidic there is no need to add any catalyst. The use of hydrochloric gas has one advantage over paratoluene sulfonic acid and that is that at the end of the reaction it canberemoved by flushing out with nitrogen, whereas there is no reasonably convenient means available of removing the paratoluene sulfonic acid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the gas through at an exceedingly slow rate so as to keep the reaction mass acidic. Only a trace of acid need be present. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material. Mypreference, however, is to use'no catalyst whatsoever and to insure complete dryness of the diol as described in the final procedure just preceding Table 3.

The products obtained in Part 1 preceding may contain a, basic catalyst. As a general procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is'required to neutralize the residual catalyst. The mixture is shaken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separated in a phase-separating trap. As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterifioation. If there is any further deposition of sodium chloride during the reflux stage; needless to say a second filtration may be required. In

any event the neutral" or slightly acidic solution of the oxypropylated derivatives described in ester from an anhydride such as phthalic anhydride, no water is eliminated. However, if it is obtained from diglycollic acid, for example, water is eliminated. All such procedures are conventional and. have been so thoroughly described in the literature that further consideration will be limited to a few examples and a comprehensive table.

Other procedures for eliminating the basic residualcatalyst, if any, can be employed. For example, the oxyalkylation can be conducted in absence of a solvent or the solvent removed after oxypropylation. Such oxypropylation end product can then be acidified with just enough concentrated hydrochloric acid to just neutralize the residual basic catalyst. To this product one can then add a small amount of anhydrous sodium sulfate (sufiicient in quantity to take up any Water that is present) and then subject the mass to centrifugal force so as to eliminate the hydrated sodium sulfate and probably the sodium chloride formed. The clear somewhat viscous straw-colored amber liquid so obtained may contain a small amount of sodium sulfate or sodium chloride but, in any event, is perfectly acceptable foresterification in the manner described.

It is to be pointed out that the products here described are not polyesters in the sense that there is a plurality of both diol radicals and acid radicals; the product is characterized by having only one diol radical.

In some instances and, in fact, in many instances I have found that in spite of thedehydration methods employed above that a mere trace of Water still comes through and that this mere trace of water certainly interferes with the acetyl or hydroxyl value determination, at least when a number of conventional procedures are used and may retard esterification, particularly where there is no sulfonic acid or hydrochloric acid. present as a catalyst. Therefore, I have preferred to use the following procedure: I have employed about 200 grams of the diol as-described in Part 1, preceding; I have added about 60 grams of benzene, and then refluxed this mixture in the glass resin pot using a phase-separating trap until the benzenecarried out all the water present as water of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of 130 to possibly 150C. When all this water or moisture has been removed I also Withdraw approximately 20 grams or a little less benzene and then add the required amount of the carboxy reactant and also about 150 grams of a high boiling aromatic petroleum solvent. These solvents are sold by various oil refineries and, as far as solvent effect act as if they were almost completely aromatic in character. Typical distillation data in the particular type I have employed and found very satisfactory is the following:

I, B. P., 142 C. 1111., 242 C. 5 1111., 200 C. m1., 244 C. 10 ml., 209 C. m1., 248 C. 15 ml., 215 C. ml., 252 C. 20 m1., 216C. 1111., 252 C. 25 1111., 220 C. ml., 260 C. 30'In1., 225 C. 30 ml., 264 C. 35 1111., 230 C. ml., 270 C. 40 1111., 234 C. ml., 280 C. 45 1111., 237 C. ml., 307 C.

after this material is added, refluxing is continued and, of course, is at high temperature, to wit, about to C. If the carboxy reactant is an anhydride needless to say no water of reaction appears; if the carboxy reactant is, an acid, water; of reaction should appear and should be eliminated at the'above reaction temperature. If it is not eliminated I simply separate out another or ,cc. of benzene by means of thephase-separating trap and thus raise the temperature to 180 or 190C.,'or even to 200C, if need be. My preference is not to go above about 200C. The use of such solvent is extremely satisfactory provided one does not attempt to remove thesolvent subsequently except by vacuum distillation and provided there is no objection to a little residue. Actually, when these materials are used for a purpose such as demulsification the solvent might just as wellbe allowed to remain. If the solvent is to be removed by distillation, and particularly vacuum distillation, then the high boiling-aromatic petroleum solvent might well be replaced by some moreexpensive solvent. such as decalin-or an alkylated decalin which has a rather definite'or close range boiling point. The removal of the solvent, of course, is purely a conventional procedure and requires no elaboration.

In the appended table solvent #7-3, which appears in all instances, is a mixture of 7 volumes of the aromatic petroleum solvent previously described and 3 volumes of benzene. This-was used, or a similar mixture, in the manner previously described. In a large number of similar ex: ample's' decalin has been used 'but it is my preference to use the above mentioned mixture and particularly with the preliminary step of removing all the water. If one does not intend TABLE 4 Ex NO of Amt. Esterifica- Time of Water 7 Aci'd Ester Solvent Solvent t1onTemp., Esten'fica- Out (gts) 0. tion (Hrs) (cc.)

#7-3 258 160 1% 9.5 #7-3 276 152 3% None #7-3 248 151 1 None #7-3 289 3% v 9.8 #7-3 263 219 1 None #7-3 263 168 2 1.0 #7-3 242 168 3% 6. 7 #7-3 250 6% None #73 232 154 2 None #73 253 1% 6.6 #7-3 238 1 155 2 None -.#73 237 I 152 5% 5.8 #7-3 247 143 5% None #7-3 238 137 4 None #7-3 248 140 2 5.6 #7-3 234 146 2% 0.2 #73 224 153 4% 4. 4 #7-3 234 150 9 None #7-3 223 150 5 None #7-3 240 172 5% 1 4.4 #7-3 223 147 3% 0.4 #7-3 264 239 12 2.6 #7-3 223 173 9 3.5 #7-3 226 153 5 None #7-3 220 140 5 None #7-3 230' 186 7 3. 4 #7-3 223 154 4% None #7-3 218 156 3% 3.1 #7-3 227 4% None #7-3 224 186 4% None #7-3 225 181 4% 3.2 #7-3 224 153 4% None The procedure 'for manufacturing the esters to remove the solvent my preference is to use the has been illustrated by preceding examples. If for any reason reaction does not take place in a manner that is acceptable, attention should be should be made to see if an" inorganic salt such as sodium chloride or sodium sulfate is not pre- TABLE 3 9 Mol. Amt. of I EX N0 Theo fiff} Actual Wt. Amt. of Polygga g g of Oxy M. W dr 0xyl gg gif ,233 Polyc'arboxy Reactant 22? Cmpd of C g 0 Value Actual (Grs.) am; H. V- (Grs.)

1, 048 107 159 704 194 Diglycollic Acid 73,5 1, 048 107 159 704 194 Phthalic Anhydride 81. 5 1, 048 107 159 704 194 MaleicAnhydride 54. 0 1, 048 107 159 704 194 Aconitic-Acid. 96; 0 1, 048 107 159 704 194 Oitraconic Anhydride 63, 5 1,048 107 189 1 do 1, 814 61. 7 4 1, 814 61. 7 104 l, 075 195 54.0 1, 814 61. 7 104 1, 075 195 35.7 1,814 61. 7 104 1, 075 195 63, 3 1, 814 61. 7 104 1,075 195 C1tracon1 c Acid. 40, 7 2, 550 s 43. 7 84. 9 1, 320 202 .-Diglyco11ic Acid 41. 0 2,550 43. 7 84. 9 1, 320 202 Phthalic Anhydnda. 45, 3 2, 550 43. 7 84. 9 1, 320 207- :MaleidAnhydride 30, 8 2, 550 43. 7 84. 9 1, 320 200 'Aconitic Acid 54, 3 2, 550 43. 7 84. 9- '1, 320 197 Gitraconic Anhydride. 34. 0 s, 125 35. 9 07. 9 1, 650 197 Digi c lncx idnnn; 31. 9 3, 125 35. 9 67. 9 1, 650 197 PhthallcAnhydride. 35. 2 3, 125 35. 9 67. 9 1, 650 199 MeleicAnhydnde 23, 5 3,125 35. 9 67. 9 l, 650 201 Ac0n1t1c Ac1d; 42, 5 3, 125 35. 9 67. 9 1, 650 198 Cltraconic Anhydrlde; 26. 6 3,125 35. 9 67. 9 1, 650 200 MethyleneDisahcyhc. 69 1 5, 050 22. 1 58. 2 1, 925 200 -:Diglycollic Acid 27. 0 5, 050 22. l 58. 2 1, 925 197 Phtlialic Anhydride--. 30. 2 5, 050 22. l 58. 2 1, 925 197 -Maleic Anhydride 20. 0 5, 050 22. l 58. 2 1, 925 Aconitic Acid 5, 050 22. 1 58. 2 1, 925 '0 6, 915 16. 3 51. 4 2, 170 196 Diglycollic Acid p 25.2 6, 945 16. 3 51. 4 2, 170 196 -Phthalic Auhydride. 27. 0 6, 945 16.3 51. 4 2, 170 196 Male c Acid", 17, 7 6, 945 16. 3 51.4 2, 170 196 Aconitic Acid. 1 v 31, 5 6, 945 16. 3 51.4 2, 170 204 Oitraconic'Anhydride. 20. 3

1 Sample decomposed somewhat; discarded.

cipitating out. Such salt should be eliminated, at least for exploration experimentation, and can be removed by filtering. Everything else being equal as the size of the molecule increases the reactive hydroxyl radical repersents a smaller fraction of the entire molecule and thus more difficulty is involved in obtaining complete esterification.

Evenunder the most carefully controlled conditions of oxypropylation involving comparatively low temperatures and long time of reaction there are formed certain compounds whose composition is still obscure. Such side reaction products can contribute a substantial proportion of the final cogeneric reaction mixture. Various suggestions have been made as to the nature of these compounds, such as being cyclic polymers of propylene oxide, dehydration products with the appearance of a vinyl radical, or isomers of propylene oxide or derivatives thereof, i. e., of an aldehyde, ketone, or allyl alcohol. In some instances an attempt to react the stoichiometric amount of a polycarboxy acid with the oxypropylated derivative results in an excess of the carboxylated reactant for the reason that apparently under conditions of reaction less reactive hydroxyl radicals are present than indicated by the hydroxyl value. Under such circumstances there is simply a residue of the carboxylic reactant which can be removed by filtration or, if desired, the esterification procedure can be repeated using an appropriately reduced ratio of carboxylic reactant. Even the determination of the hydroxyl value and conventional procedure leaves much to be desired due either to the cogeneric materials previously referred to, or for that matter, the presence of any inorganic salts or propylene oxide. Obviously this oxide should be eliminated. The solvent employed, if any, can be removed from the finished ester by distillation and particularly vacuum distillation. The final products or liquids are generally pale amber to amber in color, and show moderate viscosity. They can be bleached with bleaching clays, filtering chars, and the like. However, for the purpose of demulsification or the like color is not a factor and decolorization is not justified.

In the above instances I have permitted the.

solvents to remain present in the final reaction mass. In other instances I have followed the same procedure using decalini or a mixture of decalin or benzene in the same manner and ultimately removed all the solvents by vacuum distillation. Appearances of the final products are much the same as the diols before esterification and in some instances were somewhatfdarker in color and had a reddish cast and perhapssomewhat more viscous.

PART 3 Previou reference has been made to the fact that diols such as polypropylene glycol of approximately 2,000 molecular weight, for example, have been esterified with dicarboxy acids and employed as demulsifying agents. On first examination the difference between the herein described prod-.

ucts and such comparable products appears to' be rather insignificant. In fact, the difference i such that it fails to explain the fact that compounds of the kind herein described may be, and frequently are, 10%, 15% or 20% better on a quantitative basis than the simpler compound previously described, and demulsify faster and give cleaner oil in many instances. The method 116 of making such comparative tests has been described in a booklet entitled fTreating Oil Field Emulsions, used in the Vocational Training Course, Petroleum Industry Series, of the American Petroleum Institute.

The difference, of course, does not reside in the carboxy acid but in the diol. Momentarily an effort will be made to emphasize certain things in regard to the structure of a polypropylene glycol, such as polypropylene glycol of a 2000 molecular weight. Propylene glycol has a primary alcohol radical and a secondary alcohol radical. In this sense the building unit which forms polyproylene glycols is not symmetrical. Obviously, then, polypropylene glycols can be obtained, at least theoretically, in which two secondary alcohol groups are united or a secondary alcohol group is united to a primary alcohol group, etherization being involved, of course, in each instance.

Usually no effort is made to-differentiate between oxypropylation taking place, for example, at the primary alcohol unit radical or the secondary alcohol radical. Actually, when such products are obtained, such as a high molal polypropylene glycol or the products obtained in the manner herein described one does not obtain a single derivative such as HO(RO)1LH in which n has one and only one value, for instance, 14, 15 or 16, or the like. Rather, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known procedure without decomposition. The properties of such mixture represent the constribution of the various individual members of the mixture. On a statistical basis, of course, n can be appropriately specified. For practical purposes one need only consider the oxypropylation of a monohydric alcohol because in essence this is substantially the mechanism involved. Even in such instances where one is concerned with a monohydric reactant one cannot draw a single formula and say that by following such procedure one can readily obtain or or of such compound. However, in the case of at least monohydric initial reactants one can readily draw the formulas of a large number of compounds which appear in some'of the probable mixtures or can be prepared as components and mixtures which are manufactured conventionally.

Simply by Way of illustration reference is made to the De Groote, Wirtel and Pettingill Patent No. 2,549,434, dated April 1'7, 1951, the application for which was copending with my copending application Serial No. 179,400 noted above.

'However, momentarily referring again to a monohydric initial reactant it is obvious that if one selects any such simply hydroxylated compound and subjects such compound to oxyalkyla-- tion, such as oxyethylation, or oxypropylation, it becomes obvious that one is really producing a polymer of the alkylene oxides except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, .20, 30, 40, or 50 units. If such compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent which, for the sake of convenience, may be indicated as R0 (C2H4O)30H. Instead, one obtains a cogeneric mixture of closely related homologues,

, inwhich thelformula may be shown as the following, RO(CzH4O)nII, wherein n, as far as the staaeodai tistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where 12 may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental principles of condensation polymerization, by Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating'the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after timewithout difliculty, it is necessary to resort to some other method of description,.or else consider the value of n, in formulas such 'as those which have appeared previously and which appear in the claims, as representing both individual constituents in which n has a single definite value, and also with the understanding that n represents the average statistical value based on the assumption of completeness of reaction.

This may be illustrated as follows: Assume that in any particular example the molal ratio of the propylene oxide to the diol is 15 to 1. Actually, one'obtains products in which n probably varies from to 20, perhaps even further. The average value, however, is 15, assuming, as previously stated, that the reaction is complete. The product describedby the formula is best described also in terms of method of manufacture.

However, in the instant situation it becomes obvious that if an ordinary high molal propyleneglycol is compared to strings of white beads of various lengths, the diols herein employed as intermediates are characterized by the presence of a black bead, i. e., a radical which corresponds to a dihydroxylated glycerol ether as previously described, that is, for example the radical H H HCH HOE H H HCE HCH 11. and n are usually not equal. For instance, if one introduces mols of propylene oxide, n and 71. could not be equal, insofar that the nearest approach to equality is where the value of n is 18 7 and n is 8. However, even in the case of ari even number such as 20, 30, 40 or 50; it isals'o obvious that n and n" will not be equal inlight of what has been said previously. Both sides 'of the molecule are not going to. grow .with' equal rapidity, i. e., to the same size. Thus the diol herein employed is. difierentiated from polypropylene diol 2000, for example, in that (a) it carries a hetero unit, i. e., a unit other than a propylene glycol or propylene oxide unit, (b) such unit is ofiE center, and (c) the efiect of that unit, of course, must have some efiect in the range with which the linear molecules can be drawn together byhydrogenbinding or Van der Waals forces, or whatever else may be involved.

. What has been said previously can be emphasized in the following manner. It has been pointed out previously that in the last formula immediately preceding, 11. or 11. could be zero. :Under the conditions of manufacture as described in Part 1 it is extremely unlikely that n is ever zero. However, such compounds can be prepared readily with comparatively little difficulty by rev sorting to a blocking effect or reaction. For instance, if the dihydroxylated glycerol ether is esterified with a low molal acid such as acetic acid mole for mole and such product subjected to oxyalkylation using a catalyst, suchtas sodium methylate and guarding'against the presence of, any water, it becomes evident that all the propylene oxide introduced, for instance 15 to molecules per polyhydric alcohol molecule necessarily must enter at one side only. Ifs'uch product is then saponified so as to decompose the acetic acid ester and then acidified so as toliberatelthe watersoluble acetic acid and the water-insoluble diol a separation can be made and such diol then subjected to esterification as described in Part 2, preceding. Such esters, 'of course, actually represent products where either n or n is zero. Also intermediate procedures can be employed, i..se., following the same esterification step after partial oxypropylation. For instance, one .might' I oxypropylate withone-half the ultimate amount of propylene oxide to be used and then stop'the reaction. One could then convert this partial oxypropylation intermediate into an ester by reaction of one mole :of acetic'acidwith onemole of a, diol. This ester could then be oxypropylated with all the remaining propylene oxide. The final product so obtained could be saponified and. acidi fled so as to eliminate the water-soluble acetic acid and free the obviously unsymmetrical diol which, incidentally, should also be kerosene-solu- Me.-

From a practical standpoint I have found no advance in going to this extra step but it does emphasize the difference in structure between the herein described diols employed as intermediates and high molal polypropylene glycol, such as polypropylene glycol 2000.

PART 4 Conventional demulsifying agents employed in ithe'treatment of oil field emulsions are used'as.

such, or after dilution with anysuitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol,

denatured alcohol, propyl alcohol, butyl alcohol,:

hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc.,- may with conventional demulsifying agents.

aeoaaei .be employed as .diluentsx. Similarly, the material or. materials employed as the demulsifying agent of my process may be .admixed with one or more of the .solvents customarily used in connection Moreover, said material or materials may be used alone orin admixture with other suitable wellknown classes of demulsifying agents.

. It is;well known that conventional demulsifying agentsmay be used in a water-soluble form, or inanl oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of l to 10,000, or 1 to. 20,000, or 1 to.30,000, or even 1 to 40,000, or 1 to 50,000. as in desalting practice, such an apparent insolubility. in oil and water is not sig-! niflcant because said reagents undoubtedly have solubility. within such condensations. This same faceistruein regard to the material or materials employed as the demulsifying agentof my process; 1 a In..practicing myv process for. resolving. petroleum emulsions of the water-in-oil type, a treating. agent or demulsifying. agent of the kind above described is brought into contactwith or caused. to act upon theemulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone. or in combination with other demulsifying procedure, such as the electrical dehydration process.

.One. typeof procedure is to accumulate a volume of emulsified. oil ina tank and conduct a batch. treatment type .of. demulsification procedureto recover cleanoil- In this procedure the emulsion is admixedwith thedemulsifier, for exampleby agitating the tank of. emulsion and slowly, dripping demulsifier into. the, emulsion. In.

some cases mixing. is achieved by heating the emulsion while. dripping in the demulsifier, de-. pending upon. the convection currents in the emulsion to produce satisfactory admixture. .In axthird modification. of this type-of treatment, a circulating pump withdraws emulsion from, c. -g., thebottom of .the tank, andreintroduces it into the-top of the tank, the demulsifier being added, for example, at the suction side of said circulating pump.

In a .secondtype of treating procedure, the demulsifier is. introduced. into the well fluids at thewell-head .or at. some point between the. wellhead and the final oil storage tank, by meansof an. adjustable proportioning. mechanism or proportioning pump. )Ordinarily the flow of fluids through the subsequent lines and fittings suflices toproduce the desired degree of mixing of demulsifler and emulsion, althoughin some instances. additional mixing devices may be introduced into,

likewise. be. incorporated in any of the treating procedures described herein. I

Azthird type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier eitherperiodically or continuously in diluted or undiluated form into the well and to allow it to come to the surface with the well fluids, and then toflow. the chemicalized emul-v sion t hrough any desirable surface equipment,

20 such as employed in the othertreating proce, dures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidification of calcareous oilbearing strata, especially if suspended in or dissolved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing description, the broad process consists simply in introducing a relatively small proportion of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or through special apparatus, with or without theapplication of heat, and allowing the mixture to Stand quiescent until the undesirable water content of the emulsion separates and settles from the mass.

The following is a typical installation.

A reservoir to hold the demulsifier of the kind described (diluted or undiluted) is placed at the well-head where the efiluent liquids leave the well. This reservoir or container, which may vary from 5 gallons to 50 gallons for convenience, is connected to a proportioning pump which injects the demulsifier drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the flowline into a settling tank. The settling tank consists of a tank of any convenient size, for instance, one which will hold amounts of fluid produced in 4 to 24 hours (500 barrels to 2000 barrels capacity), and in which there is a perpendicular conduit from the top of the tank to almost the very bottom so as to permit the incoming fluids to pass from the top of the, settling tank to the bottom, so that such incoming fluids do not disturb stratification whichtakes place during the course of demulsiflcation. The settling tank has two outlets, one being below the water level to drain off the water resulting from demulsification or accompanying the emulsion as freewater, the other being an oil outlet at the top to permit the passage. of

dehydrated oil to a second tank, being a storage. tank, which holds pipeline or dehydrated oil. If

desired, the conduit or pipe line serves to carry the fluids from the well to the settling tankmayinclude a section of pipe with bafiles to serve as a mixer, to insure thorough distribution of the demulsifier throughout the fluids, or a heater for raising the temperature of the fluids to some con-. venient temperature, for instance, to F;, or both heater and mixer.

Demulsiflcation procedure is started by simply setting the pump so as to feed a comparatively large ratio of demulsifier, for instance, 1:5,000. As soon as a complete break or satisfactory demulsiflcation is obtained, the pump is regulated until experience shows that the amount of demulsifier being added is just sufficient to produce clean or dehydrated oil. The amount being fed at such stage is usually l:10,000, 1115,000, 20,000, or the like. 7

In many instances the oxyalkylated products herein specified as demulsifiers can be 'conven iently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing '75 parts by weight of an oxyalkylated derivative, for example, the product of Example 281) with 15 parts by weight of xylene and 10 parts'by weight of isopropyl alcohol, an excellent demulsifier-is obtained. :Selection of the solvent will vary, depending upon the solubility characteristics ofthe oxyalkylated product, and of course will be d ta d i a y con mic considerations. .1. e.,: OOStr'. 1

As noted above, the products hereindescribed may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is, the following: i

Oxyallgzlated derivative, for example, the productof Example 28b,,20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;.

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petro-;

PART 5 Previous reference has been made to other oxyalkylating agents other than propylene oxide, such as ethylene oxide. Obviously variants can be prepared which do not depart from what is said herein but do produce modifications. The diol derived by etherization of glycerol in the manner described can be reacted with ethylene oxide in modest amount and then subjected to oxypropylation provided that the resultant derivative is (a) water-insoluble, (b) kerosene-soluble, and (c) has present 15 to 80 alkylene oxide radicals. Needless to say, in order to have waterinsolubility and kerosene-solubility the large majority must be propylene oxide; Other variants suggest themselves, as, for example, replacing propylene oxide by butylene oxide.

More specifically then one mole of such etherized glycerol of the kind described can be treated with 2, 4 or 6 moles of ethylene oxide and then treated with propylene oxide so as to produce a water-insoluble, kerosene-soluble diol in which there are present 15 to 80 oxide radicals as previously specified. Similarly the propylene oxide can be added first and then the ethylene oxide, or random oxyalkylation can be employed using a mixture of the two oxides. The compounds so obtained are readily esterified in the same manner as described in Part 2, preceding. Incidentally, the diols described in Part 1 or the modifications described therein can be treated with various reactants such as glycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic anhydride, ethylene imine, etc. If treated with epichlorohydrin or monochloroacetic acid the resultant product can be further reacted with a tertiary amine such as pyridine, or the like, to give quaternary ammonium compounds. If treated with maleic anhydride to give a total ester the resultant can be treated with sodium bisulfite to yield a sulfosuccinate. Sulfo groups can be introduced also by means of a sulfating agent as previously suggested, or by treating the chloroacetic acid resultant with sodium sulfite.

I have found that if such hydroxylated compound or compounds are reacted further so as to produce entirely new derivatives, such new derivatives have the properties of the original hydroxylated compound insofar that they are eifective and valuable demulsifying agents for resolution of water-in-oil emulsions as found in the petroleum industry, as break inducers in doctor treatment of sour crude, etc.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subject-1 ing the emulsion to the action of a demulsifier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following'formula ,1

I 1151i Booowntiwcane)nogo clmo)fl tia c0.011

in which n and n are numerals including 0 with the proviso that n plus n equals a sum varying from 15 to 80, and n" is a whole number not over 2, R is a hydrocarbon radical having less than 8 carbon atoms, and R is a radical of the polycarboxy acid a 1 coon cooHh in which n" has its previous significance; and with the further proviso that the parent diol prior to esterification be water-insoluble and kerosene-soluble.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subject-- ing the emulsion to the action of a demulsifier including hydro phile 1 synthetic products; 'said' ized by the following formulal n E n" HooC),wRO(0 CaHo)flO](E1[%-O(CaHtO)n'CR(CO0H),."

hydrophile synthetic products being: character-- in which n and n are numerals includin 0 with the proviso that n plus n equals a sum varying from 15 to 80, and n" is a Whole number not over 2, R is a hydrocarbon radical having less than 8 carbon atoms, and R is a radical of the polycarboxy acid oooH in which n and n are numerals including 0 with the proviso that 11. plus 12 equals a sum varying from 15 to 80, and n" is a whole number not over 2, R is a hydrocarbon radical having less than 8 carbon atoms, and R is a radical of the polycarboxy acid COOH in which n has its previous significance; said 'polycarboxy' acid havingv not more. than 8 car bon. atoms; v and withthe furtherproviso that the parent diol prior towesterification be water-im.

solubleandikerosene-soluble. s

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsi fier including hydrophile synthetic products; said hydrophile synthetic products being characterized by the following formula 0 Him 7 in which n and n are numerals excluding 0 with the proviso that n plus n equals a sum varying from 15 to 80; R' is a hydrocarbon radical having less than 8 carbon atoms, and R is a radical of the dicarboxy acid coon QOOH said dicarboxy-acid having not more than 8 carbon atoms; and with the further proviso that theparent diol prior to esterification be waterinsolubleand kerosene-soluble.

5. The process of claim 4 wherein R has at least 3 carbon atoms.

6. The process of claim 4 wherein R has at least 3 carbon atoms and is derived from a watersoluble alcohol.

2-4 7. 'rheprocess of. claim 4 wherein R has at least 3 carbon atoms, is derived from a water-s soluble alcohol, and the dicarboxy acid is phthalic acid.

8. The process ofclaim 4 wherein R has at least 3 carbon atoms, is derived from a watersoluble alcohol, and the dicarboxy acid is maleic acid.

9. The process of claim 4 wherein R has at least 3 carbon atoms, is derived from a watersoluble alcohol, and the dicarboxy acid is succinic acid. 7

10. The process of claim 4 wherein R has at least 3 carbon atoms, is derived from a'watersoluble alcohol, and the dicarboxy acid is citraconic acid.

11. The process of claim 4 wherein R has at least 3 carbon atoms, is derived from a watersoluble alcohol, and the dicarboxy acid is diglycollic acid. I

MELVIN DE GROOTE.

REFERENCES CITED The following: references are of recordin the,

fil Ofethis atent UNITED STATES PATENTS Number. a e at 507 560, De G e v-f-s- May 1950 2,514,399 Kirkpatricket a1. July 11,1951

- -1.-i- -v.-- -'::r '-i---- 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING CHARACTERIZED BY THE FOLLOWING FORMULA 